Introduction to Organic Chemistry

723 Pages·2015·19.1 MB·English

by  William H. Brown

Introduction to
Organic Chemistry
SIXTH EDITION
WILLIAM H. BROWN THOMAS POON
Beloit College Claremont McKenna College
Scripps College
Pitzer College
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Library of Congress Cataloging-in-Publication Data
Brown, William Henry, 1932-
Introduction to organic chemistry. — 6th edition / William H. Brown,
Beloit College, Thomas Poon, Claremont McKenna College, Scripps
College, Pitzer College.
pages cm
Includes index.
ISBN 978-1-118-87580-3 (pbk.)
1. Chemistry, Organic. I. Poon, Thomas, 1968- II. Title.
QD253.2.B76 2016
547—dc23
2015033008
978-1119-10696-8 (BRV)
978-1119-23373-2 (EVAL Version)
Printed in the United States of America.
10 9 8 7 6 5 4 3 2 1
To Carolyn,
with whom life is a joy
Bill Brown
To Cathy and Sophia,
for a lifetime of adventures
Thomas Poon
ABOUT THE AUTHORS
WILLIAM H. BROWN is Professor Emeritus at Beloit College, where he was twice
named Teacher of the Year. He is also the author of two other college textbooks: Organic
Chemistry 5/e, coauthored with Chris Foote, Brent Iverson, and Eric Anslyn, published in
2009, and General, Organic, and Biochemistry 9/e, coauthored with Fred Bettelheim, Mary
Campbell, and Shawn Farrell, published in 2010. He received his Ph.D. from Columbia
University under the direction of Gilbert Stork and did postdoctoral work at California
Institute of Technology and the University of Arizona. Twice he was Director of a Beloit
College World Affairs Center seminar at the University of Glasgow, Scotland. In 1999, he
retired from Beloit College to devote more time to writing and development of educational
materials. Although officially retired, he continues to teach Special Topics in Organic
Synthesis on a yearly basis.
Bill and his wife Carolyn enjoy hiking in the canyon country of the Southwest. In addi-
tion, they both enjoy quilting and quilts.
THOMAS POON is Professor of Chemistry in the W.M. Keck Science Department of
Claremont McKenna, Pitzer, and Scripps Colleges, three of the five undergraduate institu-
tions that make up the Claremont Colleges in Claremont, California. He received his B.S.
degree from Fairfield University (CT) and his Ph.D. from the University of California, Los
Angeles under the direction of Christopher S. Foote. Poon was a Camille and Henry Dreyfus
Postdoctoral Fellow under Bradford P. Mundy at Colby College (ME) before joining the faculty
at Randolph‐Macon College (VA) where he received the Thomas Branch Award for Excellence
in Teaching in 1999. He was a visiting scholar at Columbia University (NY) in 2002 (and again
in 2004) where he worked on projects in both research and education with his late friend and
mentor, Nicholas J. Turro. He has taught organic chemistry, forensic chemistry, upper‐level
courses in advanced laboratory techniques, and a first‐year seminar class titled Science of Identity.
His favorite activity is working alongside undergraduates in the laboratory on research problems
involving the investigation of synthetic methodology in zeolites, zeolite photochemistry, natural
products isolation, and reactions of singlet oxygen.
When not in the lab, he likes to play guitar and sing chemistry songs to his students and
to his daughter Sophie.
iv
CONTENTS OVERVIEW
11 Covalent Bonding and Shapes 1122
Aldehydes and Ketones 396
of Molecules 1
22 1133
Acids and Bases 40 Carboxylic Acids 437
33 1144
Alkanes and Cycloalkanes 61 Functional Derivatives of Carboxylic
Acids 468
44
Alkenes and Alkynes 103
1155
Enolate Anions 504
55
Reactions of Alkenes and Alkynes 123
1166
Organic Polymer Chemistry 542
66
Chirality: The Handedness of
1177
Molecules 160 Carbohydrates 563
77 1188
Haloalkanes 190 Amino Acids and Proteins 595
88 1199
Alcohols, Ethers, and Thiols 226 Lipids (Online Chapter) 624
99 2200
Benzene and Its Derivatives 266 Nucleic Acids (Online Chapter) 648
1100 2211
Amines 313 The Organic Chemistry of Metabolism
(Online Chapter) 672
1111
Spectroscopy 341
v
CONTENTS
Covalent Bonding and Shapes
Alkanes and Cycloalkanes 61
11 33
of Molecules 1
1.1 How Do We Describe the Electronic 3.1 What Are Alkanes? 62
Structure of Atoms? 2
3.2 What Is Constitutional Isomerism in
1.2 What Is the Lewis Model Alkanes? 64
of Bonding? 5
3.3 How Do We Name Alkanes? 66
1.3 How Do We Predict Bond
3.4 What Are Cycloalkanes? 71
Angles and the Shapes of
Molecules? 13 3.5 How Is the IUPAC System of
Nomenclature Applied to
1.4 How Do We Predict If a Molecule
Molecules that Contain Functional
Is Polar or Nonpolar? 17
Groups? 72
1.5 What Is Resonance? 18
3.6 What Are the Conformations
1.6 What Is the Orbital Overlap of Alkanes and Cycloalkanes? 73
Model of Covalent Bonding? 21
3.7 What Is Cis–Trans Isomerism in
1.7 What Are Functional Cycloalkanes? 80
Groups? 26
3.8 What Are the Physical Properties of Alkanes
Summary of Key Questions 31 and Cycloalkanes? 84
Quick Quiz 32 3.9 What Are the Characteristic Reactions
Problems 34 of Alkanes? 87
Looking Ahead 38 3.10 What Are the Sources of Alkanes? 88
Group Learning Activities 39 Summary of Key Questions 91
Quick Quiz 92
CHEMICAL CONNECTIONS
Key Reactions 93
1A Buckyball: A New Form
Problems 93
of Carbon 16
Looking Ahead 98
Group Learning Activities 99
Putting it T ogether 99
CHEMICAL CONNECTIONS
Acids and Bases 40
22
3A The Poisonous Puffer Fish 81
3B Octane Rating: What T hose Numbers at the
2.1 What Are Arrhenius Acids Pump Mean 90
and Bases? 41
2.2 What Are Brønsted–Lowry Acids
and Bases? 42
2.3 How Do We Measure the Strength
Alkenes and Alkynes 103
of an Acid or Base? 44 44
2.4 How Do We Determine the Position
of Equilibrium in an Acid–Base
Reaction? 46 4.1 What Are the Structures and Shapes
of Alkenes and Alkynes? 105
2.5 What Are the Relationships
between Acidity and Molecular 4.2 How Do We Name Alkenes and
Structure? 48 Alkynes? 107
2.6 What Are Lewis Acids 4.3 What Are the Physical Properties of Alkenes
and Bases? 52 and Alkynes? 115
Summary of Key Questions 55 4.4 Why Are 1–Alkynes (Terminal Alkynes) Weak
Acids? 116
Quick Quiz 56
Key Reactions 57 Summary of Key Questions 117
Problems 57 Quick Quiz 118
Looking Ahead 59 Problems 118
Group Learning Activities 60 Looking Ahead 122
Group Learning Activities 122
vi
CONTENTS vii
CHEMICAL CONNECTIONS Summary of Key Questions 179
4A Ethylene, a Plant Growth Regulator 104 Quick Quiz 180
4B Cis–Trans Isomerism in Vision 106 Problems 181
4C Why Plants Emit Isoprene 115 Chemical Transformations 185
Looking Ahead 186
Group Learning Activities 186
Putting it Together 187
Reactions of Alkenes and Alkynes 123
55 CHEMICAL CONNECTIONS
6A Chiral Drugs 178
5.1 What Are the Characteristic Reactions
of Alkenes? 123
5.2 What Is a Reaction Mechanism? 124
5.3 What Are the Mechanisms of Electrophilic 77 Haloalkanes 190
Additions to Alkenes? 130
5.4 What Are Carbocation Rearrangements? 140
5.5 What Is Hydroboration–Oxidation of an 7.1 How Are Haloalkanes Named? 191
Alkene? 143 7.2 What Are the Characteristic Reactions
5.6 How Can an Alkene Be Reduced to an of Haloalkanes? 193
Alkane? 145 7.3 What Are the Products of Nucleophilic Aliphatic
5.7 How Can an Acetylide Anion Be Used to Create Substitution Reactions? 195
a New Carbon–Carbon Bond? 148 7.4 What Are the S 2 and S 1 Mechanisms for
N N
5.8 How Can Alkynes Be Reduced to Alkenes and Nucleophilic Substitution? 197
Alkanes? 150 7.5 What Determines Whether S 1 or S 2
N N
Predominates? 201
Summary of Key Questions 151
7.6 How Can S 1 and S 2 Be Predicted Based on
Quick Quiz 152 N N
Experimental Conditions? 206
Key Reactions 153
7.7 What Are the Products of β‐Elimination? 208
Problems 154
7.8 What Are the E1 and E2 Mechanisms for
Looking Ahead 158 β‐Elimination? 211
Group Learning Activities 158 7.9 When Do Nucleophilic Substitution and
β‐Elimination Compete? 214
CHEMICAL CONNECTIONS
5A Catalytic Cracking and the Importance Summary of Key Questions 217
of Alkenes 127 Quick Quiz 218
Key Reactions 218
Problems 219
Chemical Transformations 223
Chirality: The Handedness Looking Ahead 224
66
of Molecules 160 Group Learning Activities 225
CHEMICAL CONNECTIONS
6.1 What Are Stereoisomers? 161
7A The Environmental Impact of
6.2 What Are Enantiomers? 161 Chlorofluorocarbons 193
6.3 How Do We Designate the Configuration 7B The Effect of Chlorofluorocarbon Legislation
of a Stereocenter? 166
on Asthma Sufferers 216
6.4 What Is the 2n Rule? 168
6.5 How Do We Describe the Chirality
of Cyclic Molecules with Two
Stereocenters? 172
6.6 How Do We Describe the Chirality of 88 Alcohols, Ethers, and T hiols 226
Molecules with Three or More
Stereocenters? 174
6.7 What Are the Properties of Stereoisomers? 174 8.1 What Are Alcohols? 227
6.8 How Is Chirality Detected in the 8.2 What Are the Characteristic Reactions
Laboratory? 175 of Alcohols? 232
6.9 What Is the Significance of Chirality in the 8.3 What Are Ethers? 245
Biological World? 176 8.4 What Are Epoxides? 249
6.10 How Can Enantiomers Be Resolved? 177 8.5 What Are T hiols? 253
viii CONTENTS
8.6 What Are the Characteristic Reactions 10.5 What Are the Reactions of Amines
of T hiols? 256 with Acids? 325
Summary of Key Questions 257 10.6 How Are Arylamines Synthesized? 327
Quick Quiz 258 10.7 How Do Amines Act as
Key Reactions 259 Nucleophiles? 328
Problems 260 Summary of Key Questions 330
Chemical Transformations 264 Quick Quiz 331
Looking Ahead 264 Key Reactions 331
Group Learning Activities 265 Problems 332
Chemical T ransformations 337
CHEMICAL CONNECTIONS
Looking Ahead 337
8A Nitroglycerin: An Explosive and a Drug 230
Group Learning Activities 338
8B Blood Alcohol Screening 245
Putting it T ogether 338
8C Ethylene Oxide: A Chemical Sterilant 253
CHEMICAL CONNECTIONS
10A Morphine as a Clue in the Design
and Discovery of Drugs 314
10B The Poison Dart Frogs of South
Benzene and Its Derivatives 266
99
America: Lethal Amines 319
9.1 What Is the Structure of Benzene? 267
9.2 What Is Aromaticity? 270
9.3 How Are Benzene Compounds Named, and Spectroscopy 341
1111
What Are T heir Physical Properties? 273
9.4 What Is a Benzylic Position, and How Does It
Contribute to Benzene Reactivity? 276 11.1 What Is Electromagnetic Radiation? 342
9.5 What Is Electrophilic Aromatic 11.2 What Is Molecular Spectroscopy? 344
Substitution? 278
11.3 What Is Infrared Spectroscopy? 344
9.6 What Is the Mechanism of Electrophilic
11.4 How Do We Interpret Infrared
Aromatic Substitution? 279
Spectra? 347
9.7 How Do Existing Substituents on Benzene Affect
11.5 What Is Nuclear Magnetic
Electrophilic Aromatic Substitution? 288
Resonance? 358
9.8 What Are Phenols? 296
11.6 What Is Shielding? 360
Summary of Key Questions 303
11.7 What Is a 1H-NMR Spectrum? 360
Quick Quiz 304
11.8 How Many Resonance Signals Will
Key Reactions 304 a Compound Yield in Its 1H‐NMR
Problems 305 Spectrum? 362
Chemical Transformations 310 11.9 What Is Signal Integration? 365
Looking Ahead 311 11.10 What Is Chemical Shift? 366
Group Learning Activities 312 11.11 What Is Signal Splitting? 368
11.12 What Is 13C‐NMR Spectroscopy,
CHEMICAL CONNECTIONS
and How Does It Differ from 1H‐NMR
9A Carcinogenic Polynuclear Aromatics Spectroscopy? 371
and Cancer 277
11.13 How Do We Solve an NMR
9B Capsaicin, for Those Who Like It Hot 300 Problem? 374
Summary of Key Questions 378
Quick Quiz 380
Problems 381
1100 Amines 313 Looking Ahead 394
Group Learning Activities 395
CHEMICAL CONNECTIONS
10.1 What Are Amines? 313
11A Infrared Spectroscopy: A Window on Brain
10.2 How Are Amines Named? 316
Activity 348
10.3 What Are the Characteristic Physical Properties
11B Infrared Spectroscopy: A Window on Climate
of Amines? 319
Change 354
10.4 What Are the Acid–Base Properties of
Amines? 321 11C Magnetic Resonance Imaging (MRI) 371